Sizing of textile yarn



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United States Patent SIZING 0F TEXTILE YARN Charles P. McClelland, Brlarclilf Manor, N.Y., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed Feb. 20, 1957, Ser. No. 641,234

27 Claims. (Cl. 117--138.8)

This invention relates to the sizing of textile yarn. In one aspect this invention relates to the process of sizing textile yarn. A further aspect of this invention is directed to sized yarn and articles of manufacture resulting therefrom.

Though the manufacture of a textile fabric is mainly a series of mechanical operations, treatment with various chemicals are deemed necessary either to assist the meohanical operation or to protect the fibers or yarn from damage or imperfections. During the weaving process, wherein the textile yarn is converted into cloth or fabric, it is desirable to protect the textile fibers from the abrasive action of the moving parts of the loom. In order to accomplish this, the longitudinal yarns, more commonly called warp yarns, are protected by sizing with a film-forming material to prevent damage. This size, once it has fulfilled its purpose, is usually washed out of the cloth. The transversed yarns, that is woof or weft yarns, of the cloth, are not ordinarily sized since they are subjected to little or no abrasive action from the loom.

Materials commonly used for sizing textile yarns are film-forming materials such as starch and gelatin for the older fibers, i.e., cotton, wool, rayon and the like, and more recently materials such as polyvinyl alcohol, carboxymethyl cellulose, polyacrylic acid, hydroxyethylated starch which are chiefly used on the new synthetic fibers such as nylon Orlon Dacron Dynel and others well recognized to the art. These conventional filmforming agents are modified by additional agents to make them suitable as warp sizes. In some cases the films are quite weak, such as with starch, and materials such as natural gums are added to increase its strength. Starch and the other materials lack lubricating properties and generally have added to them various waxes and oils to act as lubricants during the weaving process. Many of the sizing materials form films which'are too brittle and must be plasticized or softened by adding humectants such as a glycol and glycerine or cationic softeners such as amine fatty acid condensates. In many cases, the adhesion of the film-forming materials to the fibers is poor and small amounts of active solvents or of surface active agents must be added to improve this property. In the case of starch, which is almost universally used in cotton sizing, the size material is hard to prepare since it must be cooked in order to form a suitable dispersion for application to the yarn and, since it is insoluble in water, it must be removed after the weaving operation 1 Generic term for a series of polyainide resins made by the polymerization of a. hexamethylene diamine salt or adlpic a cid.

E. I. du Pont de Nemours & Co. trademark for a synle fiber made princl ally from (polyacr lonitrile.v E. I. du Pont de emours 8: o. tra emark for a synthetic fiber made by the condensation of dimethyl terephthalate and eth lene glycol.

Unlon Carb tie and Carbon Corporations name for synthetic fibers made by the copclymerlzation of acrylonitrile and vinyl chloride. 7

25,980,556 Patented Apr. 18, 1961 ICE -When employing poly(ethylene oxide) as the sole sizing ingredient an additional advantage accrues in that the poly(ethylene oxide), once applied to the textile yarn, can be conveniently removed by virtue of its watersoluble characteristic.

Accordingly, one or more of the following objects will be achieved by the practice of my invention. It is an object of this invention to provide a novel process for sizing textile yarn. It is also an object of this invention to provide a novel process for sizing textile yarn with a sizing amount of an aqueous solution comprising poly- (ethylene oxide). Another object of this invention is the sizing of yarns, threads, filaments, fibers and the like, with a sizing amount of poly(ethylene oxide) as the sole sizing ingredient, or poly(ethylene oxide) in admixture with a non-volatile polyethylene glycol or starch. A further object of this invention is the production of cloth woven from yarn which yarn has been sized with a sizing amount of poly(ethylene oxide) as the sole sizing ingredient; or poly(ethylene oxide) in admixture with polyethylene glycol or starch. Other objects will become apparent to those skilled in the art in the light of the instant specification.

The water-soluble ethylene oxide polymers contemplated herein are those having a reduced viscosity from about 1 to about 60 and higher. Polymers with reduced viscosities from about 1 to about 30 are preferred. As is known, reduced viscosity, a value obtained by dividing the specific viscosity by the concentration of the polymer in the solution, the concentration being measured in grams of polymer per m1. of solvent, is regarded as a measure of molecular weight. The specific viscosity is obtained by dividing the difference between the viscosity of the solution and the viscosity of the solvent by the viscosity of the solvent. The reduced viscosities herein referred to are measured at a concentration of 0.2 gram of polymer in 100 ml of acetonitrile at 30 C.

Poly(ethylene oxide) with a reduced viscosity from about 1.0 to about 60 and greater can be made by a variety of processes. A number of catalysts can be used to effect the polymerization reaction. Among these are a number of pure metal carbonates such as calcium, strontium, barium and manganous carbonate which preferably are in a form containing at least about 0.1 percent by weight of sorbed water and preferably are substantially free of non-sorbed water. The alkaline earth metal carbonates are preferably used in a concentration from about 0.3 to 3 percent by weight based on the ethylene oxide to be polymerized, and manganous carbonate is preferably used inconcentrations of the order of 0.1 percent by weight based on the ethylene oxide to be polymerized. The polymerization reaction is preferably carried out at a temperature in the range of from 90 C. to C. The production of poly(ethylene oxide) by the use of such carbonates is the subject matter of the application by F. N. Hill and F. E. Bailey, Jr., entitled Polymerization of Epoxides, Serial No.'587,933, filed May 26, 1956, now abandoned, and assigned to the same assignee as the present invention.

The derivatives obtained by reacting an alkaline earth metal with organic hydroxy compounds can also be used to polymerize ethylene oxide to produce polymers with reduced viscosities of about 1.0 and greater. Such materials a strontium methylate, calcium glycoxide, barium phenolate, the calcium derivative of Z-methoxymethanol, and the calcium derivative of diethylene glycol are satisfactory catalysts for the polymerization reaction. Care should be taken to avoid inactivation of these catalysts by reactive gases such as moist air. Catalysts such as these can be used in a concentration in the range from about 0.1 to about 2.0 percent by weight of the ethylene oxide to be polymerized While employing a reaction temperature, preferably in the range from about 90 C. to about 150 C. The process is the subjectmatte; of the application of F. N. Hill, I. T. Fitzpatrick, and F. E. Bailey, In, entitled Polymerizationof. Epoxides Using Alkaline Earth Metal DCIiVQliVSQOf. Q1'8iiglC. HyQOXy Compounds and New Compositions Qbtained Thereby, Serial No. 587,954, filed May 29,1956, now abandoned, and assigned to the sanie assignee as the present invention.

7 The hexammoniates and amidesof the alkaline earth metals and the decomposition products of the hexammoniates which contain the alkaline earth metal, nitrogen, and hydrogen are particularly well adapted to producing poly(ethylene oxide) with a reduced viscosity greater than 30 when measured in a concentration of 0.2 gram of. polymer per 100 ml. of solution in acetonitrile at 30 C.

The hexammoniates can be made by reacting the appropriate alkaline earth metal with liquid ammonia. A solid is recovered by allowing the unreacted ammonia to evaporate. On standing, While protected from reactive gases or vapors, the solid decomposes to give an amide as an ultimate product. Methods for making the hexammoniates and amides are found in the articles of Bergstrom and Fernelius in Chem. Revs. 12, 43 (1933) and in Chem. Revs. 20, 413 (1937). These catalysts should be carefully protected from reactive gases (the hexammoniates are pyrophoric) during preparation and in all operations after preparation. These catalysts are preferably employed in concentrations in the range from about 0.02 percent to 10 percent by weight based on the ethylene oxide charged while employing a reaction temperature preferably in the range from about 0 C. to 60 'C. The process is the subject matter of the application of F. N. Hill, I. T. Fitzpatrick and F. E. Bailey, Jr., entitled Polymerization of Epoxides and New Products Obtained Thereby, Serial No. 587,955, filed May 29, 1956, now abandoned, and assigned to the same assignee as the'present invention. A

The ethylene oxide polymers throughout he range of reduced viscosities from about 1.0 to about 60 and greater,

are water soluble. They appear to form homogeneous systems with water in all proportions. The water solubility characteristic of poly(ethylene oxide) is of particular advantage; textile yarn treated with the novel sized material of this invention and woven into fabric can be waterwashed, necessary to remove the poly(ethylene oxide) size therefrom. The ethylene oxide polymers produced by the above methods show little change in melting point with increased molecular .weight and the melting point, as measured by change of stiffness with temperature,

'is found to be about 65:2" C. throughout the range 4 ing a reduced viscosity from about 1.0 to about 60 and greater. In particular, impurities such as excessive water, oxygen, carbon dioxide and aldehydes should not be present in the monomeric feed.

The sized material of this invention, as stated previously, is applicable to synthetic and natural fibers such as cotton, wool, rayon, silk, acetate rayon, Orlon, nylon, Dacron, Dynel and the like. Poly (ethylene oxide) size is a strong, flexible, resinous material. The sizing solution is prepared by dissolving in water poly(ethylene oxide) having a reduced viscosity from about 1 to about 60 and greater, and preferably from about 1 to about 30. Once the weaving operation is finished the water-soluble poly(ethylene oxide) size is removed by washing in water or a soap and water solution. If desired, the size can be left on the fabric and thus, assumes the role of a finishing agent. The sized material exhibits, among other desirable features, little or no flakingor shedding during the weaving operation, and no stickiness, which is an undesirable feature of some types of sizing materials. It has anextremely low biological oxygen demand, which is a desirable feature of warp sizes since stream pollution has become a serious factor in modern textile mill op erations. Additionally, it is more eificient than most conventional sizing materials because smaller amounts will perform effectively as a size. ide) is water-soluble, it has surprisingly low-moisture.- pickup in dry form. For example, the poly(ethylene oxide) contemplated in my invention is substantially as fiexible'at 25 percent relative humidity as it is at percent relative humidity- Consequently, exacting humidity control ove'r the Weavingroom is not necessary.-

In general, the poly(ethylene oxide), contemplated by my invention is employed as a warp size agent for tentile yarn, since the weft yarn does'not" usually require a sizing agent. However, if necessary, both Weft and warp yarns can be coated or impregnated with my novel sizecomposition.

The size solution can be prepared by adding poly- (ethylene oxide) having a reduced viscosity from about 1 to about 60 and greater, to water, at ambient room temperature. In general, the solution viscosity is in the range from about centipoises to about 15,000 centipoises, preferably from about 1,000 centipoises to about 6,000 centipoises. The manner of'preparing the size solution is not narrowly critical, and agitation means such asa slow speed paddle will effect solution of the water-soluble polyrriers- Conventional wetting agents such as Tergitol TMN polyethylene glycol alkyl ether and others well recognized in the art can be employed. For suitable results the percent by weight of poly(ethylene oxide) size on the sizedyarn is governed by several 'factors such as economic consideration, type and weight of the yarn fibers, time of size treatment, the reduced viscosity of the 'size, the viscosity of the size solution employed the pressure on the squeeze rolls and the temperature of the drying cansof the slasher, the particular weave in which the yarn is to be woven, etc. For example, when weaving cloth with cotton yarn, advantageous results are obtained if the concentration of the size inthe aqueous solution is such that from about 1 toabout 6 percent by weight, and higher of poly(ethylene oxide) having a reduced viscosity of approximately 1 and higher is deposited on the yarn prior to weaving. In general, a fine yarn requires more percent by weight of size, based on the'weight of the yarn treated, than a heavier yarn. It is advisable and convenient to apply the size solution having a "solution viscosity from about 100 centipoises to about 1'5',000'centipoises, preferably from about 1,000 centipoises to about 6,000 centipoises,

at. ambientroom remperamrajr approximately 70 F.,

however, lower and highertemperatures,'i.e., up to Though -poly,(ethylene oxstarch, gelatin and others, to form a combined sizing agent having some of the advantageous propertiesof the poly(ethylene oxide) itself. Poly(ethylene oxide) increases the toughness and lubricity of these other filmforming agents, and in many cases improves their solubility in water and reduces their biological oxygen de mand.

As is well-recognized water-soluble, non-volatile polyethylene glycol is not suitable for use as a size agent by itself. I have discovered, quite surprisingly indeed, tlnit polyethylene glycol having a molecular weight range from about 400 to about 15,000 can be dissolved in an aqueous solution containing the above-described ethylene oxide polymers, i.e., possessing a reduced viscosity in acetonitrile of at least one, to give a suitable size formulation for synthetic and natural yarn such as cotton, Dacron, Orlon, Dynel, rayon, etc. Satisfactory results are obtained by dissolving in said aqueous solution up to 60 percent by weight, based on the poly(ethylene oxide), of polyethylene glycol. In general, this size solution can have a solution viscosity in the range from about 500 to about 10,000 centipoises, and higher, and preferably from 1,000 to about 6,000 centipoises, at ambient room temperature, i.e., approximately 70 F. Lower temperatures and temperatures up to 190 F. are satisfactory providing that the solution viscosity falls Within the above-mentioned range and that molecular degradation of the poly(ethylene oxide) is substantially avoided.

Admixtures of poly(ethylene oxide) and up to 60 percent by weight of polyethylene glycol based on the poly- (ethylene oxide) are somewhat incompatible; however, the use of such admixtures as a size agent is apparently uneffected. The incompatibility characteristic becomes more pronounced with admixtures containing greater than 60 percent by weight of polyethylene glycol,,based on the poly(ethylene oxide), and consequently, such ,ad-

mixtures lose their usefulness as size agents.

Further embodiments of the instant invention contemplates the use of admixtures of poly(ethylene oxide) and corn starch or hydroxyethylated starches such as Penford Gum 6 260 as satisfactory size agents to textile yarn. An aqueous size agent comprising poly(ethylene oxide) and up to 90 percent by weight of corn starch or a hydroxyethylated starch, based on the poly(ethylene oxide) gives satisfactoryresults. The aqueous size agent can be prepared by cooking the starch in an aqueous medium until dispersion of the starch occurs, and subsequently adding the water-soluble poly(ethylene oxide). The aqueous admixture can be agitated to facilitate the dissolving of said poly(ethylene oxide) in the aqueous medium. In general, the aqueous admixture comprising poly(ethylene oxide) and corn starch can have a solution viscosity in the range from about 100 to about 5,000 centipoises, and higher, and preferably from about 100 to about 2,000 centipoises, at ambient room temperature, i.e., about 70 F. Satisfactory results are likewise obtained when employing as a size agent an aqueous admixture comprising poly(ethylene oxide) and an hydroxyethylated starch having a-solution viscosity range from about 100 to about 1,000 at ambient room temperature. Temperatures lower than 70 F. and as high as 190 F. are satisfactory providing that the solution viscosity is within the above-mentioned ranges and that Patrick and Ford trademark to: hydroxyethylated starch.

the quantity of size which they choose to '6 molecular degradation of the poly(ethylene oxide) is substantially avoided.

As stated previously, the weight of size (dry), based on the weight of yarn, necessary for suitable results is governed by various factors. I have found, in general, that Dynel yarn sized with about 5 to about 20 percent by weight of poly(ethylene oxide) is satisfactory whereas cotton yarn size with about 1 to about 6 percent by weight of poly(ethylene oxide) gives suitable results. When employing poly(ethylene oxide) and polyethylene glycol as the size agent, cotton yarn may be effectively sized with aboutv 2.5 to about 7.0 percent by weight. Cotton yarn sized with about 3.5 to 10 percent by weight of poly(ethylene oxide) and corn starch gives suitable results.

It is to be understood, however, that this invention is i not to be construed as limited to the size ranges as illustrated above. Workers skilled in the textile field, given the teachings of this disclosure, can readily determine the quantity of size suitable for a particular yarn under the particular conditions of operation. Accordingly, the term a sizing amoun as used in the specification, including the appended claims, means a suffioient percent by weight of dry size, based on the weight of the yarn, to effectively size said yarn. As stated above, workers familiar with the textile industry can readily determine apply to the textile yarn.

The following examples are illustrative.

EXAMPLE I To a sealed round-bottomed flask equipped with a thermowell and a magnetic stirrer was charged 1 kg. of

heptane, 333 g. of ethylene oxide and 4.83 g.'of calcium amide. The reaction mixture was stirred for 17 hours without external heating or cooling; the temperature varied from '16 to 32 C. The product was filtered off and vacuum-dried. The amount of product was 96 grams. After exposing the product to air to decompose any unreacted catalyst, it showed a reduced viscosity, of 50.

EXAMPLE II EXAMPLE III A. Preparation of strontium methylate Strontium metal, 50 grams in amount, cut into small pieces, was placed in a 2liter creased flask equipped with a nitrogen inlet and vent for the nitrogen, condenser and feed tank, and washed with cc. of methanol of 99.5 percent by weight minimum purity and containing a maximum of 0.002 percent by weight of acetone. The flask was purged with nitrogen. The wash methanol was removed from the flask by suction and discarded. Fresh methanol, 600 cc. in amount, was added to the strontium metal and allowed to react with stirring. The reaction was complete in about 2 hours, at which time the flask was transferred to a dry box under a nitrogen atmosphere and .the solid precipitation of strontium methylate filtered off. The precipitate was bottled under nitrogen and used in the following preparation of poly(ethylene oxide).

B. Polymerization of ethylene oxide Two small glass tubes were each loaded in a dry box under a nitrogen atmosphere with 20 mg. of the strontium methylate from the preparation described in A, above,

and approximately 30 grams of ethylene oxide. The tubes were sealed and then placed in a water bath maintained at a temperature of 100 C. and agitated. After 16 hours at this temperature, 95 to 98 percent of the ethylene oxide was converted to a polymer having a reduced viscosity in acetonitrile of 3.0.

EXAMPLE IV Varying concentrations of aqueous poly(ethylene oxide) solution having a reduced viscosity of approximately were applied to a low-twist cotton yarn using a Model 51 Calloway slasher. A single cotton yarn with'a 3.75 twist multiplier was employed because a fine yarn with a soft twist will give a more critical test of; the properties of the sizing agent. The poly(ethylene oxide) dissolved in water, was applied'as a warp size to a yard band of ends of yarn using various temperatures of application, various concentrations of poly(ethylene oxide) in the size box (disclosed in Table I), and various degrees of wet pickup. The yarn was dried on 4' cylinders set consecutively attemperatures of: 150 F., 170 F., 200 F., and 170 F. and was wound onto a spool using a minimum of tension.

A standard starch size was used 'as a control sample. A 5 percent solution of a 40 fluidity starch size containing 6 percent, based on the weight of the starch, of More,

tex Compound 85 as a softener and lubricant was cooked 1 /2 hours at 212 F. and then applied to the same low-twist cotton yarn using the Calloway slasher at a concentration normally used in industrial practice. The size box was maintained at a temperature of 200 F. and the drying cylinders were set at 200 F., 250 F., and 230 F. respectively.

The various samples of yarn that had been sized on the Calloway slasherwere tested on the warp shed tester. This tester is an instrument designed to simulate all the actions of a loom except the laying in and beating up of the filling yarn by the shuttle and reed. The tester consists of a tension controlled let-off spool, two sets of harnesses and heddles, a reed, an up-beat motion, drop wires, and a take-up mechanism. The mechanical motion of the various parts simulates a loom operation of 176 picks per minute. The band of 60 ends of sized yarn, approximately 20 yards in length, was passed through the shed. tester in four hours. A pan at the bottom of the instrument was used to catch the shed which might fall from the wrap yarn due to the abrasive action of moving parts of the instrument. This shed is expressed as percent by weight of the total weight of the yarn sample which passes through the tester. The number of warp ends which broke during the test were also recorded and are expressed as the number of ends down per hour. The results are set out in Table I below Table 1 EVALUATION OF POLY(ETHYLENE OXIDE) SIZED COTTON YARN Size 80- Shed Tester lution, Temp.o Yarn Size Run Percent Solution Content, 7

By F.) Percent Shed, Ends Weight By Wt. Percent Down-Per By Wt. Hour -starch sample. Weaving test sample.

K proprietary fatty oil ttiier.

'Ihe-resultsof the poly(ethylene oxide) size carried out on the warp shed tester, as disclosed in Table I, compare favorably with a conventional starch size as a control. The important properties are the percentage of shed and the ends down per hour, the latter property in particular, in'relation to the amount of size applied on the weight of the yarn. It wll be noted, for example, in run 6 that poly- (ethylene oxide) sized cotton yarn shows low shed values (1.95) and very low ends down per hour (0.25) at a concentration as low as 1.46 percent by weight of poly(ethylene oxide) based on the weight of the yarn. A starched sized yarn (run 1) with almost six times as much size (8.52%) showed a shed of 1.57 percent and ends down per'hour of- 1.25. Run 13, the weaving test sample, discloses the results-of the cotton yarn impregnated with 3.30 percent by weight ofthe size. It is pointed out that the shed value (0.79) and ends down per hour (0.25) are ex tremely satisfactory. The cotton yarn impregnated in the manner disclosed in run 13 (Example IV) was tested in an actual weaving trial. The results are setout in Example VI below.

EXAMPLE V The'procedure, equipment and cotton yarn employed in Example IVwere followedin the following runs. The reduced viscosity of the poly(ethylene oxide) ranged from 5 to 60; note first vertical column of Table II. The temperature of the sizing solution was approximately 72 F. The results are set out in Table II below.

Table II EVALUATION OF POLY (ETHYLENE OXIDE) SIZED COTTON YARN Solution Size Shed Tester Re- Conduced tent, Run Vis- Conc., Vis- Per- Shed, Ends cosity Percosity cent Per- Down cent (cps) By W t. cent For By Wt. By Wt Hour 1 Starch sample.

The results of the poly(ethylene oxide) size carried out on the warp shed tester, Table II, compare favorably with a conventional starch size as a control. It is pointed out that the amount of poly(ethylene oxide) size, i.e., size content on the yarn, fifth vertical column, deposited on the cotton yarn was, in all the runs except run 11, far less than th'e'quantity of starch deposited on the cotton yarn. In general, the ends down per hour was zero or a satisfactory low value when employing poly(ethylene oxide) as the size. The shed values are likewise satisfactory, though of dmportancei with a 3.75 twist multiplier using a 80 by 80 print cloth. Each 9 EXAMPLEVI An aqueous solution of poly(ethylene oxide) at 70 F. containing 3 percent by weight of poly(ethylene oxide) based on the solution, and having a reduced viscosity of approximately 5, was applied to a 30-single cotton yarn Model 51 Calloway slasher. The yarn contained a final size weight of 3.3 percent based on the weight of the yarn. The band of sized warp yarn was dried on cylinders set at 150 F., 170 F., 200 F., and 170 F. After slashing, the yarns were beamed and placed on a Draper X-D loom operating at 172 picks per minute. The fabric woven was 36 inches wide and had a plain weave construction of 72 x 72. The ends down per hour were approximately 4.0 which is equal to or better than a conventional starched size yarn woven under comparable conditions.

EXAMPLE v11 Poly(ethylene oxide) having a reduced viscosity of 3.8 was applied to a 30 single cotton yarn. The yarn was slashed on a five-cylinder Cocker'slasher at 8 yards per minute. The sized yarn was subsequently woven into an run consisted of 40 yards of warp with the loom running at 168 picks per minute (40 yards being approximately equivalent to 100,000 picks). The results are set out in Table III below.

Table III Yarn Size Commercial Loom Size 80- Size Content Run lution, Bath (Dry Pick- Percent 'Iemp., up). Per- Shed, Ends By Wt. F. cent By Percent Down Wt. By Wt. Per Hour EXAMPLE VIII In this example an aqueous solution of poly(ethylene oxide) having a reduced viscosity of approximately was applied as a warp sizing agent for Dynel synthetic fiber, i.e., vinyl chloride/acrylonitrile copolymer. Dynel 55 below.

that cotton yarn sized with conducted at ambient room temperahumidity as contrasted with the com breakage and shedding occurs.

10. fiber, like many of the newer synthetic fibers, presents a problem of sizing, in that its surface contains a large number of short highly resilient fibers, which, unless cfficiently lubricated and bound by the sizing agent, entangle during the weaving processes and cause breakage of the yarn. The poly(ethylene oxide) was applied to Dynel yarn on a Model 51 Calloway slasher at F. The yarn was dried at temperatures between F. and 200 F. Results of the percent shed of the size and ends golwn per hour of the yarn are set forth in Table IV e ow.

l Penick and Ford trademark for liydroxyethylated starch; 77% by weight oi total size ingredients.

2 E. I. du Pont de Nemours & Co. trademark for polyvinyl alcohol; 18% by weight of total size ingredients.

Seydel-Wooley & Co. trademark for blend of natural and synthetic fats and. waxes; 5% by weight of total size ingredients.

Poly(ethylene oxide) applied as a size to Dynel fiber not only has good adhesion as indicated by little or no flaking, but appears to lubricate and bind the short fibers comprising Dynel yarn and thus, effectively prevents entanglement and gives free low yarn breakage. Runs 2 and 3 show very low valuesregarding percentage shed of the size and the ends down per hour of the yarn 1ndicating excellent performance. A comparison with a conventionally compounded size made from Penform Gum, Elvanol 51-05, and Seyco Wax C, run 1 of Table IV shows that even with large quantities of this size yarn In comparison, run 3 with poly(ethylene oxide) shows better performance with a lower quantity of size.

EXAMPLE IX Various sizing formulations were applied to a Burlington Dacron yarn in the manner set forth in Example IV using the Model 51 Calloway slasher. A 30 singles Dacron yarn, 3 denier, 1% inch staple-was employed. The various samples of yarn that had been sized on the Calloway slasher were tested on the warp shed tester described previously. The results are set out in Table V Table V Solution Composition, Per- Shed Tester cent by Wt 1 Temp. of Solution Yarn Size Run Solution Viscosity Content Poly- Polyeth- F.) (cps) (Percent Shed Ends (ethylene Penford ylene by Wt.) (Percent Down oxide) Gum Glycol y Wt.) Per Hour . 1 Poly(ethylene oxide) haying a reduced viscosity of 3.8.

7 Polyethylene glycol having a molecular weight of approximately 6,000.

Poly(ethylene oxide) having a reduced viscosity of 30. t A hydroxyethylated starch.

5 Recommended size formulation containing (based on weight of total size ingredients):

% by weight oihydroxyethylated starch; 22% by weight of polyvinyl alcohol; 9% by weight 69 0f blend of natural and synthetic fats and waxes.

12 sation of dimethyl terephthalate and ethylene glycol.

7. The process of claim 3 wherein said aqueous solution has a solution viscosity in the range from about 1,000 centipoises to about 6,000 centipoises.

the ends down per hour figures d Perce Shed (Where 5 8. 'In a process of sizing textile yarn, the improvement recorded). which comprises sizing said yarn with an aqueous solu- These results compare favorably Wlth the recomtion comprising poly(ethylene oxide) and a polyethylene mended size formulation (footn te 5 l u the glycol, said poly(ethylene oxide) having a reduced visry weight pickup of the recommended size formulation cosity in acetonitrile of at least one, and said poly- WaS much greater than the novel e formulatlofls) 0f ethylene glycol'having a molecular weight in the range this invention. from about 400'to about 15,000.

EXAMPLE X 9. The process of claim 8 wherein said aqueous solu- In this example several experiments were conducted tion has a solution viscqsity in the range from about employing as a size poly(ethylene oxide) per se, or in 500 to about 3 I Q PQ S- admixture with cornstarch or polyethylene glycol. Corn 0. The process of claim 9 wherein ,sald polyethylene starch was used as a control. The size formulations were glycol is employed in an amount up. to about 60 percent applied to a 30-single cotton yarn using the Calloway by weight, based ontlgle weight of the poly(ethylene 0xslasher described above, and the various samples of sized ide). yarn were then tested on the Warp shed tester also de- .11. The process of-claim lO wherein said textile yarn scribed previously. The results are set out in Table VI is cotton. below. 12. The process of claim 1-0'whereinsaid textile yarn Table VI Solution Composition, Per- Shed Tester cent by Wt.

Temp. of Solution Yarn Size Run Solution Viscosity Content Poly- Poly- F.) (cps) (Percent Shed Ends (ethylene Corn ethylene by Wt.) (Percent Down oxide) Starch Glycol by Wt.) Per Hour 70 784 4. 6 0. s2 0. 2s 180 152 s. 2 0. 69 0. 160 300 9. 0 1.11 0. on 70 2, 200 2. 7 0. 78 0.00 160 3,500 8.8 0.15 200 11.0 o 50 0. 0o

1 Poly (ethylene oxide) having a reduced viscosity of 3.8. 2 Poly (ethylene oxide) having a reduced viscosity of 30. 3 Polyethylene glycol having a molecular weight of approximately 6,000. It is pointed out that .the novel size formulations of 40 is manufactured from fibers produced by the polymerithis invention, i.e., poly(ethylene oxide) alone or in admixture with. corn starch or polyethylene glycol, when applied to the cotton yarn, give satisfactory results when tested on the shed tester for percent shed, and the number of ends down per hour.

It is also noticed that the dry Weight pickup on the cotton yarn when employing corn starch as the size is greater than is, the case with thenovel size formulations of this invention.

It is obvious that various modifications, of this invention can bemade without departing from the spirit and scope thereof.

What is claimed is: v

1. In a process of sizing textile yarn,the improvement which comprises sizing said yarn with anaqueous soluiton comprising poly(ethylene oxide), said poly(ethylene oxide),having a reduced viscosity in acetonitrile of at least one.

2. In a process of sizing textile yarn, the improvement which comprises applying to said yarn an aqueous solution comprising poly(ethylene oxide), said poly(ethylene oxide) having a reduced viscosity in acetonitrile in the range from about 1 to 60, and said aqueous solution possessing a solution viscosity in the range from about 100 centipoises to about 15,000 centipoises.

3. The process of claim 2 wherein the poly(ethylene oxide) has a reduced viscosity in acetonitrile in the range from about 1 to about 30.

4. The process of claim 3 wherein the textile yarn is cotton.

5. The process of claim 3 wherein the textile yarn is manufactured from fibers produced by the polymerization of vinyl chloride and acrylonitrile.

6. The process of claim 3 wherein the textile yarn is manufactured from fibers produced by the condenzation of vinyl chloride and acrylonitrile.

13. The process of claim 10 wherein said textile yarn is manufactured from fibers produced by the condensation of dimethyl terephthalate andvethylene glycol.

14. In a process of sizing textile yarn, the improvement which comprises sizing said yarn with an aqueous medium containing poly(ethylene oxide) and starch, said starch being employed in an amount up to about percent by weight, based on the weight of said poly(ethylene oxide), and said poly(ethylene oxide) having a reduced viscosity in acetonitrile of at least one.

15. The process of claim 14 wherein said starch is corn starch.

16. The process of claim 15 wherein said aqueous medium has a solution viscosity in the range from about to about 5,000 centipoises.

17. The process of claim 14 wherein said starch is an hydroxyethylated starch.

18. The process of claim 17 wherein said aqueous medium has a solution viscosity in the range from about 100 toabout 1,000 centipoises.

19. An article of manufacture comprising textile yarn selected from the group consisting of natural and synthetic fibers sized with a sizing amount of a water-soluble poly(ethylene oxide) having a reduced viscosity in acetonitrile greater than one.

20. The article of manufacture of claim 19 wherein the textile yarn is cotton.

21. The article of manufacture of claim 19 wherein the textileyarn is manufactured from fibers produced by the polymerization of vinyl chloride and acrylonitrile.

23. An article of manufacture comprising textile yarn selected from the group consisting of natural and synthetic fibers sized with a sizing amount of a mixture of poly(ethylene oxide) and polyethylene glycol, said poly- (ethylene oxide) having a reduced viscosity in acetonitrile of at least one, said polyethylene glycol having a molecular weight in the range from about 400 to about 15,000 and said mixture containing up to 60 percent by weight of polyethylene glycol, based on the weight of poly(ethylene oxide).

24. An article of manufacture comprising textile yarn sized with a sizing amount of a mixture of poly(ethylene oxide) and starch, said poly(ethylene oxide) having a reduced viscosity in acetonitrile of at least one, and said mixture containing up to 90 percent -by weight of starch, based on the weight of poly(ethylene oxide).

25. The article of manufacture of claim 24 wherein said starch is corn starch, and said yarn is a natural yarn.

said starch is an hydroxyethylated starch, and said yarn is a synthetic yarn.

27. The article of manufacture of claim wherein said yarn is cotton.

, References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Carbowarf Compoundand Polyethylene Glycols, June 30, 1946, Carbide and Carbon Chem. Corp., New York, NY. 7 a v 

1. IN A PROCESS OF SIZING TEXTILE YARN, THE IMPROVEMENT WHICH COMPRISES SIZING SAID YARN WITH AN AQUEOUS SOLUTION COMPRISING POLY(ETHYLENE OXIDE), SAID POLY(ETHYLENE OXIDE) HAVING A REDUCED VISCOSITY IN ACETONITRILE OF AT LEAST ONE. 